Aerosol propellants comprising unsaturated fluorocarbons

ABSTRACT

Disclosed herein are propellants comprising fluorocarbons and/or hydrofluorocarbons. Also disclosed are sprayable compositions comprising the propellants.

CROSS REFERENCE TO RELATED APPLICATION(S)

This application claims the benefit of priority to U.S. application Ser.No. 11/590,344 filed Oct. 30, 2006, and claims the benefit of priorityto U.S. Provisional Application No. 60/732,292, the complete disclosureof which is incorporated herein by reference.

FIELD OF THE INVENTION

Disclosed herein are aerosol propellant compositions comprisingunsaturated fluorocarbons or unsaturated hydrofluorocarbons. Alsodisclosed is the use of these compositions in preparing aerosolproducts.

BACKGROUND OF THE INVENTION

In the early 1970s, concern began to be expressed that the stratosphericozone layer (which provides protection against penetration of theEarth's atmosphere by ultraviolet radiation) was being depleted bychlorine atoms introduced to the atmosphere from the release ofchlorofluorocarbons. These chlorofluorocarbons were used as propellantsin aerosols, as blowing agents for foams, as refrigerants and ascleaning/drying solvent systems. Because of the great chemical stabilityof fully halogenated chlorofluorocarbons, according to the ozonedepletion theory, these compounds do not decompose in the Earth'stroposphere but reach the stratosphere where they slowly degradeliberating chlorine atoms which in turn react with the ozone.

Concern reached such a level that in 1978 the U.S. EnvironmentalProtection Agency (EPA) placed a ban on nonessential uses of fullyhalogenated chlorofluorocarbons (CFC) as aerosol propellants, and in1995 banned nonessential uses of hydrochlorofluorocarbon (HCFC)propellants.

There is also a demand for aerosol propellants which have significantlyless photochemical reactivity than hydrocarbons that contribute to theformation of ambient ozone and ground level smog. These compounds aretypically referred to as low-VOC (volatile organic compound) or non-VOC.

The disclosure herein relates to the discovery of compositions, whichinclude unsaturated fluorocarbons and hydrofluorocarbons. Thesecompositions have zero ozone depletion potential (ODP), low globalwarming potential (GWP) and are lower VOC than hydrocarbons. Thesecompositions are useful as pure components or in mixtures. Thesecompositions are used as aerosol propellants.

SUMMARY OF THE INVENTION

One aspect is for a propellant comprising at least one fluorocarbon orhydrofluorocarbon selected from the group consisting of:

-   -   (i) a hydrofluorocarbon having the formula E- or Z—R¹CH═CHR²,        wherein R¹ and R² are, independently, C₁ to C₆ perfluoroalkyl        groups; or    -   (ii) a fluorocarbon or hydrofluorocarbon selected from the group        consisting of CF₃CF═CHF, CF₃CH═CF₂, CHF₂CF═CF₂, CHF₂CH═CHF,        CF₃CF═CH₂, CF₃CH═CHF, CH₂FCF═CF₂, CHF₂CH═CF₂, CHF₂CF═CHF,        CHF₂CF═CH₂, CF₃CH═CH₂, CH₃CF═CF₂, CH₂FCHCF₂, CH₂FCF═CHF,        CHF₂CH═CHF, CF₃CF═CFCF₃, CF3CF₂CF═CF₂, CF₃CF═CHCF₃,        CF₃CF₂CF═CH₂, CF₃CH═CHCF₃, CF₃CF₂CH═CH₂, CF₂═CHCF₂CF₃,        CF₂═CFCHFCF₃, CF₂═CFCF₂CHF₂, CHF₂CH═CHCF₃, (CF₃)₂C═CHCF₃,        CF₃CF═CHCF₂CF₃, CF₃CH═CFCF₂CF₃, (CF₃)₂CFCH═CH₂, CF₃CF₂CF₂CH═CH₂,        CF₃(CF₂)₃CF═CF₂, CF₃CF₂CF═CFCF₂CF₃, (CF₃)₂C═C(CF₃)₂,        (CF₃)₂CFCF═CHCF₃, CF₂═CFCF₂CH₂F, CF₂═CFCHFCHF₂, CH₂═C(CF₃)₂,        CH₂CF₂CF═CF₂, CH₂FCF═CFCHF₂, CH₂FCF₂CF═CF₂, CF₂═C(CF₃)(CH₃),        CH₂═C(CHF₂)(CF₃), CH₂═CHCF₂CHF₂, CF₂═C(CHF₂)(CH₃),        CHF═C(CF₃)(CH₃), CH₂═C(CHF₂)₂, CF₃CF═CFCH₃, CH₃CF═CHCF₃,        CF₂═CFCF₂CF₂CF₃, CHF═CFCF₂CF₂CF₃, CF₂═CHCF₂CF₂CF₃,        CF₂═CFCF₂CF₂CHF₂, CHF₂CF═CFCF₂CF₃, CF₃CF═CFCF₂CHF₂,        CF₃CF═CFCHFCF₃, CHF═CFCF(CF₃)₂, CF₂═CFCH(CF₃)₂, CF₃CH═C(CF₃)₂,        CF₂═CHCF(CF₃)₂, CH₂═CFCF₂CF₂CF₃, CHF═CFCF₂CF₂CHF₂,        CH₂═C(CF₃)CF₂CF₃, CF₂═CHCH(CF₃)₂, CHF═CHCF(CF₃)₂,        CF₂═C(CF₃)CH₂CF₃, CH₂═CFCF₂CF₂CHF₂, CF₂═CHCF₂CH₂CF₃,        CF₃CF═C(CF₃)(CH₃), CH₂═CFCH(CF₃)₂, CHF═CHCH(CF₃)₂,        CH₂FCH═C(CF₃)₂, CH₃CF═C(CF₃)₂, CH₂═CHCF₂CHFCF₃, CH₂C(CF₃)CH₂CF₃,        (CF₃)₂C═CHC₂F₅, (CF3)₂CFCF═CHCF₃, CH₂═CHC(CF₃)₃,        (CF₃)₂C═C(CH₃)(CF₃), CH₂═CFCF₂CH(CF₃)₂, CF₃CF═C(CH₃)CF₂CF₃,        CF₃CH═CHCH(CF₃)₂, CH₂═CHCF₂CF₂CF₂CHF₂, (CF₃)₂C═CHCF₂CH₃,        CH₂═C(CF₃)CH₂C₂F₅, CH₂═CHCH₂CF₂C₂F₅, CH₂═CHCH₂CF₂C₂F₅,        CF₃CF₂CF═CFC₂H₅, CH₂═CHCH₂CF(CF₃)₂, CF₃CF═CHCH(CF₃)(CH₃),        (CF₃)₂C═CFC₂H5, cyclo-CF₂CF₂CF₂CH═CH—, cyclo-CF₂CF₂CH═CH—,        CF₃CF₂CF₂C(CH₃)═CH₂, CF₃CF₂CF₂CH═CHCH₃, cyclo-CF₂CF₂CF═CF—,        cyclo-CF₂CF═CFCF₂CF₂—, cyclo-CF₂CF═CFCF₂CF₂CF₂,        CF₃CF₂CF₂CF₂CH═CH₂, CF₃CH═CHCF₂CF₃, CF₂CF₂CH═CHCF₂CF₃,        CF₃CH═CHCF₂CF₂CF₃, CF₃CF═CFC₂F₅, CF₃CF═CFCF₂CF₂C₂F₅,        CF₃CF₂CF═CFCF₂C₂F₅, CF₃CH═CFCF₂CF₂C₂F₅, CF₃CF═CHCF₂CF₂C₂F₅,        CF₃CF₂CH═CFCF₂C₂F₅, CF₃CF₂CF═CHCF₂C₂F₅, C₂F₅CF₂CF═CHCH₃,        C₂F₅CF═CHCH₃, (CF₃)₂C═CHCH₃, CF₃C(CH₃)═CHCF₃, CHF═CFC₂F₅,        CHF₂CF═CFCF₃, (CF₃)₂C═CHF, CH₂FCF═CFCF₃, CHF═CHCF₂CF₃,        CHF₂CH═CFCF₃, CHF═CFCHFCF₃, CF₃CH═CFCHF₂, CHF═CFCF₂CHF₂,        CHF₂CF═CFCHF₂, CH₂CF═CFCF₃, CH₂FCH═CFCF₃, CH₂═CFCHFCF₃,        CH₂═CFCF₂CHF₂, CF₃CH═CFCH₂F, CHF═CFCH₂CF₃, CHF═CHCHFCF₃,        CHF═CHCF₂CHF₂, CHF₂CF═CHCHF₂, CHF═CFCHFCHF₂, CF₃CF═CHCH₃,        CF₂═CHCF₂Br, CHF═CBrCHF₂, CHBr═CHCF₃, CF₃CBr═CFCF₃,        CH₂═CBrCF₂CF₃, CHBr═CHCF₂CF₃, CH₂═CHCF₂CF₂Br, CH₂═CHCBrFCF₃,        CH₃CBr═CHCF₃, CF₃CBr═CHCH₃, (CF₃)₂C═CHBr, CF₃CF═CBrCF₂CF₃,        E-CHF₂CBr═CFC₂F₅, Z—CHF₂CBr═CFC₂F₅, CF₂═CBrCHFC₂F₅,        (CF₃)₂CFCBr═CH₂, CHBr═CF(CF₂)₂CHF₂, CH₂═CBrCF₂C₂F₅,        CF₂═C(CH₂Br)CF₃, CH₂═C(CBrF₂)CF₃, (CF₃)₂CHCH═CHBr,        (CF₃)₂C═CHCH₂Br, CH₂═CHCF(CF₃)CBrF₂, CF₂═CHCF₂CH₂CBrF₂,        CFBr═CHCF₃, CFBr═CFCF₃, CF₃CF₂CF₂CBr═CH₂, and CF₃(CF₂)₃CBr═CH₂.

A further aspect is for a sprayable composition comprising theabove-described propellant. Preferably, the sprayable composition is anaerosol.

Other objects and advantages will become apparent to those skilled inthe art upon reference to the detailed description that hereinafterfollows.

DETAILED DESCRIPTION OF THE INVENTION

Applicants specifically incorporate the entire content of all citedreferences in this disclosure. Applicants also incorporate by referencethe co-owned and concurrently filed applications entitled “FireExtinguishing and Fire Suppression Compositions Comprising UnsaturatedFluorocarbons” “Solvent Compositions Comprising UnsaturatedFluorocarbons” U.S. Application 60/732,090 filed Nov. 1, 2005, and“Blowing Agents for Forming Foam Comprising Unsaturated Fluorocarbons”U.S. Application 60/732,090 filed Nov. 1, 2005, and “CompositionsComprising Fluoroolefins and Uses Thereof”, U.S. Application 60,732,581,filed Nov. 1, 2005.

Further, when an amount, concentration, or other value or parameter isgiven as either a range, preferred range, or a list of upper preferablevalues and lower preferable values, this is to be understood asspecifically disclosing all ranges formed from any pair of any upperrange limit or preferred value and any lower range limit or preferredvalue, regardless of whether ranges are separately disclosed. Where arange of numerical values is recited herein, unless otherwise stated,the range is intended to include the endpoints thereof, and all integersand fractions within the range. It is not intended that the scope of theinvention be limited to the specific values recited when defining arange.

One aspect relates to compositions useful in aerosol; i.e., pressurized,dispensing systems. The disclosure herein relates in particular to thefield of aerosol compositions which exhibit environmental responsibilitywhile retaining desirable properties associated with aerosol dispensingsystems.

There are numerous difficulties associated with formulating anenvironmentally responsible propellant for use with an aerosoldispensing system, including but not limited to achieving a singlephase, soluble composition which will retain desirable spraycharacteristics and product performance characteristics of aerosolscurrently marketed. Flammability is also a consideration. Alsoproblematic in the formulation of personal care products is obtaining acomposition useful in dispensing active ingredient from an aerosoldispensing system absent toxic side effects.

Aerosol products are generally preferred over products dispensed bypumps or other systems. Many advantages of aerosols stem from the factthat air is not drawn into the aerosol container to replace ingredientsdispensed. Thus the product is not exposed to deteriorating or oxidizingeffects of air and/or transient moisture, the product maintains itssterility, and preservatives need not be included in the productcomposition. Consumers prefer aerosols for their convenience, ease ofuse and cleanliness. Broadly speaking, the characteristics of the spraydispensed from aerosol systems are superior to those of other systems.The product composition is generally applied with a finer, more evenspray than when applied with pump sprays. Pump-type dispensers tend toover-concentrate the product in one spot because of inability tomaintain uniformity of product dispersal throughout the target area.This is important, for example, in a hairspray product where it isdesirable that the spray retain manageability and hold of the hair styleyet not weigh the hair down, give an unnatural hold, or feel sticky totouch.

It is, therefore, desirable to develop a homogeneous, soluble andnontoxic composition with limited flammability, useful in an aerosoldispensing system for personal care as well as other products, whichretains advantageous spray characteristics and other properties of anaerosol, while achieving environmental responsibility.

Accordingly, one aspect to provide a composition useful in an aerosoldispensing system which achieves the advantageous properties of anaerosol.

A further object to provide a sealed container with an aerosoldispensing system and a composition which attains the objectivesdescribed herein.

The foregoing objectives are achieved with the unsaturated fluorocarbonand hydrofluorocarbon propellant compositions disclosed herein. Thecompositions may be formulated with active ingredient from about 1-15%by weight, or more. Total propellant may vary from 15-95%.

Also contemplated is an aerosol dispensing system comprising a sealedcontainer equipped with an aerosol dispensing valve and containingtherein the composition and active ingredient as above.

An important physical property associated with the dispensing of aerosolproducts is the vapor pressure of the propellant. By “vapor pressure” ismeant the pressure exerted when a liquefied propellant gas is inequilibrium with its vapor in a closed container, such as an aerosolcan. Vapor pressure can be measured by connecting a pressure gauge tothe valve on an aerosol can or gas cylinder containing the vapor/liquidmixture. A standard of measurement of vapor pressure in the U.S. aerosolindustry is pounds per square inch gauge (psig) with the gas/liquefiedmixture at constant temperature, most commonly at 70° F. (21° C.). Thevapor pressure of liquefied gases most widely employed as aerosolpropellants will vary over the range of about 20 to 90 psig (138 to 621kPa) at 70° F. (21° C.). The propellant systems disclosed herein havevapor pressures in this range.

One aspect encompasses non-toxic compositions useful in an aerosoldispensing system. The compositions comprise unsaturated fluorocarbons(FCs) and/or hydrofluorocarbons (HFCs) alone or in mixture with eachother or other suitable propellants, including saturated HFCs,hydrocarbons (HCs), dimethylether, carbon dioxide, nitrous oxide, andnitrogen. Optional active ingredients and additives may be included inthe formulation in order to prepare different forms of end products bynumerous methods known to those skilled in the art.

One embodiment provides blowing agents having the formula E- orZ—R¹CH═CHR² (Formula I), wherein R¹ and R² are, independently, C₁ to C₆perfluoroalkyl groups. Examples of R¹ and R² groups include, but are notlimited to, CF₃, C₂F₅, CF₂CF₂CF₃, CF(CF₃)₂, CF₂CF₂CF₂CF₃, CF(CF₃)CF₂CF₃,CF₂CF(CF₃)₂, C(CF₃)₃, CF₂CF₂CF₂CF₂CF₃, CF₂CF₂CF(CF₃)₂, C(CF₃)₂C₂F₅,CF₂CF₂CF₂CF₂CF₂CF₃, CF(CF₃) CF₂CF₂C₂F₅, and C(CF₃)₂CF₂C₂F₅. Exemplary,non-limiting Formula I compounds are presented in Table 1.

TABLE 1 Code Structure Chemical Name F11E CF₃CH═CHCF₃1,1,1,4,4,4-hexafluorobut-2-ene F12E CF₃CH═CHC₂F₅1,1,1,4,4,5,5,5-octafluoropent-2-ene F13E CF₃CH═CHCF₂C₂F₅1,1,1,4,4,5,5,6,6,6-decafluorohex-2-ene F13iE CF₃CH═CHCF(CF₃)₂1,1,1,4,5,5,5-heptafluoro-4-(trifluoromethyl)pent-2-ene F22EC₂F₅CH═CHC₂F₅ 1,1,1,2,2,5,5,6,6,6-decafluorohex-3-ene F14ECF₃CH═CH(CF₂)₃CF₃ 1,1,1,4,4,5,5,6,6,7,7,7-dodecafluorohept-2-ene F14iECF₃CH═CHCF₂CF—(CF₃)₂1,1,1,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-2-ene F14sECF₃CH═CHCF(CF₃)—C₂F₅1,1,1,4,5,5,6,6,6-nonfluoro-4-(trifluoromethyl)hex-2-ene F14tECF₃CH═CHC(CF₃)₃1,1,1,5,5,5-hexafluoro-4,4-bis(trifluoromethyl)pent-2-ene F23EC₂F₅CH═CHCF₂C₂F₅ 1,1,1,2,2,5,5,6,6,7,7,7-dodecafluorohept-3-ene F23iEC₂F₅CH═CHCF(CF₃)₂1,1,1,2,2,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-3-ene F15ECF₃CH═CH(CF₂)₄CF₃ 1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluorooct-2-eneF15iE CF₃CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,4,4,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-2-ene F15tECF₃CH═CH—C(CF₃)₂C₂F₅1,1,1,5,5,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hex-2-ene F24EC₂F₅CH═CH(CF₂)₃CF₃ 1,1,1,2,2,5,5,6,6,7,7,8,8,8-tetradecafluorooct-3-eneF24iE C₂F₅CH═CHCF₂CF—(CF₃)₂1,1,1,2,2,5,5,6,7,7,7-undecafluoro-6-(trifluoromethyl)hept-3-ene F24sEC₂F₅CH═CHCF(CF₃)—C₂F₅1,1,1,2,2,5,6,6,7,7,7-undecafluoro-5-(trifluoromethyl)hept-3-ene F24tEC₂F₅CH═CHC(CF₃)₃1,1,1,2,2,6,6,6-octafluoro-5,5-bis(trifluoromethyl)hex-3-ene F33EC₂F₅CF₂CH═CH—CF₂C₂F₅1,1,1,2,2,3,3,6,6,7,7,8,8,8-tetradecafluorooct-4-ene F3i3iE(CF₃)₂CFCH═CH—CF(CF₃)₂1,1,1,2,5,6,6,6-octafluoro-2,5-bis(trifluoromethyl)hex-3-ene F33iEC₂F₅CF₂CH═CH—CF(CF₃)₂1,1,1,2,5,5,6,6,7,7,7-undecafluoro-2-(trifluoromethyl)hept-3-ene F16ECF₃CH═CH(CF₂)₅CF₃1,1,1,4,4,5,5,6,6,7,7,8,8,,9,9,9-hexadecafluoronon-2-ene F16sECF₃CH═CHCF(CF₃)—(CF₂)₂C₂F₅1,1,1,4,5,5,6,6,7,7,8,8,8-tridecafluoro-4-(trifluoromethyl)hept-2-eneF16tE CF₃CH═CHC(CF₃)₂—CF₂C₂F₅1,1,1,6,6,6-octafluoro-4,4-bis(trifluoromethyl)hept-2-ene F25EC₂F₅CH═CH(CF₂)₄CF₃1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoronon-3-ene F25iEC₂F₅CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,2,5,5,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-3-eneF25tE C₂F₅CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,6,6,7,7,7-decafluoro-5,5-bis(trifluoromethyl)hept-3-ene F34EC₂F₅CF₂CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,9-hexadecafluoronon-4-ene F34iEC₂F₅CF₂CH═CH—CF₂CF(CF₃)₂1,1,1,2,2,3,3,6,6,7,8,8,8-tridecafluoro-7-(trifluoromethyl)oct-4-eneF34sE C₂F₅CF₂CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,3,6,7,7,8,8,8-tridecafluoro-6-(trifluoromethyl)oct-4-eneF34tE C₂F₅CF₂CH═CH—C(CF₃)₃1,1,1,5,5,6,6,7,7,7-decafluoro-2,2-bis(trifluoromethyl)hept-3-ene F3i4E(CF₃)₂CFCH═CH—(CF₂)₃CF₃1,1,1,2,5,5,6,6,7,7,8,8,8-tridecafluoro-2(trifluoromethyl)oct-3-eneF3i4iE (CF₃)₂CFCH═CH—CF₂CF(CF₃)₂1,1,1,2,5,5,6,7,7,7-decafluoro-2,6-bis(trifluoromethyl)hept-3-ene F3i4sE(CF₃)₂CFCH═CH—CF(CF₃)C₂F₅1,1,1,2,5,6,6,7,7,7-decafluoro-2,5-bis(trifluoromethyl)hept-3-ene F3i4tE(CF₃)₂CFCH═CH—C(CF₃)₃1,1,1,2,6,6,6-heptafluoro-2,5,5-tris(trifluoromethyl)hex-3-ene F26EC₂F₅CH═CH(CF₂)₅CF₃1,1,1,2,2,5,5,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-3-ene F26sEC₂F₅CH═CHCF(CF₃)—(CF₂)₂C₂F₅1,1,1,2,2,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-5-(trifluoromethyl)non-3-eneF26tE C₂F₅CH═CHC(CF₃)₂—CF₂C₂F₅1,1,1,2,2,6,6,7,7,8,8,8-dodecafluoro-5,5-bis(trifluoromethyl)oct-3-eneF35E C₂F₅CF₂CH═CH—(CF₂)₄CF₃1,1,1,2,2,3,3,6,6,7,7,8,8,9,9,10,10,10-octadecafluorodec-4-ene F35iEC₂F₅CF₂CH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,2,3,3,6,6,7,7,8,9,9,9-pentadecafluoro-8-(trifluoromethyl)non-4-eneF35tE C₂F₅CF₂CH═CH—C(CF₃)₂C₂F₅1,1,1,2,2,3,3,7,7,8,8,8-dodecafluoro-6,6-bis(trifluoromethyl)oct-4-eneF3i5E (CF₃)₂CFCH═CH—(CF₂)₄CF₃1,1,1,2,5,5,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-3-eneF3i5iE (CF₃)₂CFCH═CH—CF₂CF₂CF(CF₃)₂1,1,1,2,5,5,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct-3-eneF3i5tE (CF₃)₂CFCH═CH—C(CF₃)₂C₂F₅1,1,1,2,6,6,7,7,7-nonafluoro-2,5,5-tris(trifluoromethyl)hept-3-ene F44ECF₃(CF₂)₃CH═CH—(CF₂)₃CF₃1,1,1,2,2,3,3,4,4,7,7,8,8,9,9,10,10,10-octadecafluorodec-5-ene F44iECF₃(CF₂)₃CH═CH—CF₂CF(CF₃)₂1,1,1,2,3,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-2-(trifluoromethyl)non-4-eneF44sE CF₃(CF₂)₃CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,6,6,7,7,8,8,9,9,9-pentadecafluoro-3-(trifluoromethyl)non-4-eneF44tE CF₃(CF₂)₃CH═CH—C(CF₃)₃1,1,1,5,5,6,6,7,7,8,8,8-dodecafluoro-2,2,-bis(trifluoromethyl)oct-3-eneF4i4iE (CF₃)₂CFCF₂CH═CH—CF₂CF(CF₃)₂1,1,1,2,3,3,6,6,7,8,8,8-dodecafluoro-2,7-bis(trifluoromethyl)oct-4-eneF4i4sE (CF₃)₂CFCF₂CH═CH—CF(CF₃)C₂F₅1,1,1,2,3,3,6,7,7,8,8,8-dodecafluoro-2,6-bis(trifluoromethyl)oct-4-eneF4i4tE (CF₃)₂CFCF₂CH═CH—C(CF₃)₃1,1,1,5,5,6,7,7,7-nonafluoro-2,2,6-tris(trifluoromethyl)hept-3-eneF4s4sE C₂F₅CF(CF₃)CH═CH—CF(CF₃)C₂F₅1,1,1,2,2,3,6,7,7,8,8,8-dodecafluoro-3,6-bis(trifluoromethyl)oct-4-eneF4s4tE C₂F₅CF(CF₃)CH═CH—C(CF₃)₃1,1,1,5,6,6,7,7,7-nonafluoro-2,2,5-tris(trifluoromethyl)hept-3-eneF4t4tE (CF₃)₃CCH═CH—C(CF₃)₃1,1,1,6,6,6-hexafluoro-2,2,5,5-tetrakis(trifluoromethyl)hex-3-ene

Compounds of Formula I may be prepared by contacting a perfluoroalkyliodide of the formula R¹I with a perfluoroalkyltrihydroolefin of theformula R²CH═CH₂ to form a trihydroiodoperfluoroalkane of the formulaR¹CH₂CHIR². This trihydroiodoperfluoroalkane can then bedehydroiodinated to form R¹CH═CHR². Alternatively, the olefin R¹CH═CHR²may be prepared by dehydroiodination of a trihydroiodoperfluoroalkane ofthe formula R¹CHICH₂R² formed in turn by reacting a perfluoroalkyliodide of the formula R²I with a perfluoroalkyltrihydroolefin of theformula R¹CH═CH₂.

Said contacting of a perfluoroalkyl iodide with aperfluoroalkyltrihydroolefin may take place in batch mode by combiningthe reactants in a suitable reaction vessel capable of operating underthe autogenous pressure of the reactants and products at reactiontemperature. Suitable reaction vessels include fabricated from stainlesssteels, in particular of the austenitic type, and the well-known highnickel alloys such as Monel® nickel-copper alloys, Hastelloy® nickelbased alloys and Inconel® nickel-chromium alloys.

Alternatively, the reaction may take be conducted in semi-batch mode inwhich the perfluoroalkyltrihydroolefin reactant is added to theperfluoroalkyl iodide reactant by means of a suitable addition apparatussuch as a pump at the reaction temperature.

The ratio of perfluoroalkyl iodide to perfluoroalkyltrihydroolefinshould be between about 1:1 to about 4:1, preferably from about 1.5:1 to2.5:1. Ratios less than 1.5:1 tend to result in large amounts of the 2:1adduct as reported by Jeanneaux, et al. in Journal of FluorineChemistry, Vol. 4, pages 261-270 (1974).

Preferred temperatures for contacting of said perfluoroalkyl iodide withsaid perfluoroalkyltrihydroolefin are preferably within the range ofabout 150° C. to 300° C., preferably from about 170° C. to about 250°C., and most preferably from about 180° C. to about 230° C.

Suitable contact times for the reaction of the perfluoroalkyl iodidewith the perfluoroalkyltrihydroolefin are from about 0.5 hour to 18hours, preferably from about 4 to about 12 hours.

The trihydroiodoperfluoroalkane prepared by reaction of theperfluoroalkyl iodide with the perfluoroalkyltrihydroolefin may be useddirectly in the dehydroiodination step or may preferably be recoveredand purified by distilled prior to the dehydroiodination step.

The dehydroiodination step is carried out by contacting thetrihydroiodoperfluoroalkane with a basic substance. Suitable basicsubstances include alkali metal hydroxides (e.g., sodium hydroxide orpotassium hydroxide), alkali metal oxide (for example, sodium oxide),alkaline earth metal hydroxides (e.g., calcium hydroxide), alkalineearth metal oxides (e.g., calcium oxide), alkali metal alkoxides (e.g.,sodium methoxide or sodium ethoxide), aqueous ammonia, sodium amide, ormixtures of basic substances such as soda lime. Preferred basicsubstances are sodium hydroxide and potassium hydroxide.

Said contacting of the trihydroiodoperfluoroalkane with a basicsubstance may take place in the liquid phase preferably in the presenceof a solvent capable of dissolving at least a portion of both reactants.Solvents suitable for the dehydroiodination step include one or morepolar organic solvents such as alcohols (e.g., methanol, ethanol,n-propanol, isopropanol, n-butanol, isobutanol, and tertiary butanol),nitriles (e.g., acetonitrile, propionitrile, butyronitrile,benzonitrile, or adiponitrile), dimethyl sulfoxide,N,N-dimethylformamide, N,N-dimethylacetamide, or sulfolane. The choiceof solvent may depend on the boiling point product and the ease ofseparation of traces of the solvent from the product duringpurification. Typically, ethanol or isopropanol are good solvents forthe reaction.

Typically, the dehydroiodination reaction may be carried out by additionof one of the reactants (either the basic substance or thetrihydroiodoperfluoroalkane) to the other reactant in a suitablereaction vessel. Said reaction may be fabricated from glass, ceramic, ormetal and is preferably agitated with an impellor or stirring mechanism.

Temperatures suitable for the dehydroiodination reaction are from about10° C. to about 100° C., preferably from about 20° C. to about 70° C.The dehydroiodination reaction may be carried out at ambient pressure orat reduced or elevated pressure. Of note are dehydroiodination reactionsin which the compound of Formula I is distilled out of the reactionvessel as it is formed.

Alternatively, the dehydroiodination reaction may be conducted bycontacting an aqueous solution of said basic substance with a solutionof the trihydroiodoperfluoroalkane in one or more organic solvents oflower polarity such as an alkane (e.g., hexane, heptane, or octane),aromatic hydrocarbon (e.g., toluene), halogenated hydrocarbon (e.g.,methylene chloride, ethylene dichloride, chloroform, carbontetrachloride, or perchloroethylene), or ether (e.g., diethyl ether,methyl tert-butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran,dioxane, dimethoxyethane, diglyme, or tetraglyme) by in the presence ofa phase transfer catalyst. Suitable phase transfer catalysts includequaternary ammonium halides (e.g., tetrabutylammonium bromide,tetrabutylammonium hydrosulfate, triethylbenzylammonium chloride,dodecyltrimethylammonium chloride, and tricaprylylmethylammoniumchloride), quaternary phosphonium halides (e.g.,triphenylmethylphosphonium bromide and tetraphenylphosphonium chloride),cyclic ether compounds known in the art as crown ethers (e.g.,18-crown-6 and 15-crown-5).

Alternatively, the dehydroiodination reaction may be conducted in theabsence of solvent by adding the trihydroiodoperfluoroalkane to a solidor liquid basic substances.

Suitable reaction times for the dehydroiodination reactions are fromabout 15 minutes to about six hours or more depending on the solubilityof the reactants. Typically the dehydroiodination reaction is rapid andrequires about 30 minutes to about three hours for completion.

The compound of formula I may be recovered from the dehydroiodinationreaction mixture by phase separation after addition of water, bydistillation, or by a combination thereof.

The compositions disclosed herein may comprise a single compound ofFormula I, for example, one of the compounds in Table 1, or may comprisea combination of compounds of Formula I.

In addition to the inventive compounds described above, compoundspresented in Table 2 can be used as aerosol propellants.

TABLE 2 Name Structure Chemical name HFC-1225s C₃HF₅ HFC-1225yeCF₃CF═CHF 1,2,3,3,3-pentafluoro-1-propene HFC-1225zc CF₃CH═CF₂1,1,3,3,3-pentafluoro-1-propene HFC-1225yc CHF₂CF═CF₂1,1,2,3,3-pentafluoro-1-propene HFC-1234s C₃H₂F₄ HFC-1234ye CHF₂CF═CHF1,2,3,3-tetrafluoro-1-propene HFC-1234yf CF₃CF═CH₂2,3,3,3-tetrafluoro-1-propene HFC-1234ze CF₃CH═CHF1,3,3,3-tetrafluoro-1-propene HFC-1234yc CH₂FCF═CF₂1,1,2,3-tetrafluoro-1-propene HFC-1234zc CHF₂CH═CF₂1,1,3,3-tetrafluoro-1-propene HFC-1234ye CHF₂CF═CHF1,2,3,3-tetrafluoro-1-propene HFC-1243s C₃H₃F₃ HFC-1243yf CHF₂CF═CH₂2,3,3-trifluoro-1-propene HFC-1243zf CF₃CH═CH₂ 3,3,3-trifluoro-1-propeneHFC-1243yc CH₃CF═CF₂ 1,1,2-trifluoro-1-propene HFC-1243zc CH₂FCH═CF₂1,1,3-trifluoro-1-propene HFC-1243ye CHF₂CF═CHF1,2,3-trifluoro-1-propene HFC-1243ze CHF₂CH═CHF1,3,3-trifluoro-1-propene FC-1318s C₄F₈ FC-1318my CF₃CF═CFCF₃1,1,1,2,3,4,4,4-octafluoro-2-butene FC-1318cy CF₃CF₂CF═CF₂1,1,2,3,3,4,4,4-octafluoro-1-butene HFC-1327s C₄HF₇ HFC-1327myCF₃CF═CHCF₃ 1,1,1,2,4,4,4-heptafluoro-2-butene HFC-1327ye CHF═CFCF₂CF₃1,2,3,3,4,4,4-heptafluoro-1-butene HFC-1327py CHF₂CF═CFCF₃1,1,1,2,3,4,4-heptafluoro-2-butene HFC-1327et (CF₃)₂C═CHF1,3,3,3-tetrafluoro-2-(trifluoromethyl)- 1-propene HFC-1327czCF₂═CHCF₂CF₃ 1,1,3,3,4,4,4-heptafluoro-1-butene HFC-1327cye CF₂═CFCHFCF₃1,1,2,3,4,4,4-heptafluoro-1-butene HFC-1327cyc CF₂═CFCF₂CHF₂1,1,2,3,3,4,4-heptafluoro-1-butene HFC-1336s C₄H₂F₆ HFC-1336yfCF₃CF₂CF═CH₂ 2,3,3,4,4,4-hexafluoro-1-butene HFC-1336ze CHF═CHCF₂CF₃1,3,3,4,4,4-hexafluoro-1-butene HFC-1336eye CHF═CFCHFCF₃1,2,3,4,4,4-hexafluoro-1-butene HFC-1336eyc CHF═CFCF₂CHF₂1,2,3,3,4,4-hexafluoro-1-butene HFC-1336pyy CHF₂CF═CFCHF₂1,1,2,3,4,4-hexafluoro-2-butene HFC-1336qy CH₂FCF═CFCF₃1,1,1,2,3,4-hexafluoro-2-butene HFC-1336pz CHF₂CH═CFCF₃1,1,1,2,4,4-hexafluoro-2-butene HFC-1336mzy CF₃CH═CFCHF₂1,1,1,3,4,4-hexafluoro-2-butene HFC-1336qc CF₂═CFCF₂CH₂F1,1,2,3,3,4-hexafluoro-1-butene HFC-1336pe CF₂═CFCHFCHF₂1,1,2,3,4,4-hexafluoro-1-butene HFC-1336ft CH₂═C(CF₃)₂3,3,3-trifluoro-2-(trifluoromethyl)-1- propene HFC-1345s C₄H₃F₅HFC-1345qz CH₂FCH═CFCF₃ 1,1,1,2,4-pentafluoro-2-butene HFC-1345mzyCF₃CH═CFCH₂F 1,1,1,3,4-pentafluoro-2-butene HFC-1345fz CF₃CF₂CH═CH₂3,3,4,4,4-pentafluoro-1-butene HFC-1345mzz CHF₂CH═CHCF₃1,1,1,4,4-pentafluoro-2-butene HFC-1345sy CH₃CF═CFCF₃1,1,1,2,3-pentafluoro-2-butene HFC-1345fyc CH₂═CFCF₂CHF₂2,3,3,4,4-pentafluoro-1-butene HFC-1345pyz CHF₂CF═CHCHF₂1,1,2,4,4-pentafluoro-2-butene HFC-1345cyc CH₃CF₂CF═CF₂1,1,2,3,3-pentafluoro-1-butene HFC-1345pyy CH₂FCF═CFCHF₂1,1,2,3,4-pentafluoro-2-butene HFC-1345eyc CH₂FCF₂CF═CF₂1,2,3,3,4-pentafluoro-1-butene HFC-1345ctm CF₂═C(CF₃)(CH₃)1,1,3,3,3-pentafluoro-2-methyl-1- propene HFC-1345ftp CH₂═C(CHF₂)(CF₃)2-(difluoromethyl)-3,3,3-trifluoro-1- propene HFC-1354s C₄H₄F₄HFC-1354fzc CH₂═CHCF₂CHF₂ 3,3,4,4-tetrafluoro-1-butene HFC-1354ctpCF₂═C(CHF₂)(CH₃) 1,1,3,3-tetrafluoro-2-methyl-1- propene HFC-1354etmCHF═C(CF₃)(CH₃) 1,3,3,3-tetrafluoro-2-methyl-1- propene HFC-1354tfpCH₂═C(CHF₂)₂ 2-(difluoromethyl)-3,3-difluoro-1- propene HFC-1354myCF₃CF═CFCH₃ 1,1,1,2-tetrafluoro-2-butene HFC-1354mzy CH₃CF═CHCF₃1,1,1,3-tetrafluoro-2-butene FC-141-10s C₅F₁₀ FC-141-10myyCF₃CF═CFCF₂CF₃ 1,1,1,2,3,4,4,5,5,5-decafluoro-2- pentene FC-141-10cyCF₂═CFCF₂CF₂CF₃ 1,1,2,3,3,4,4,5,5,5-decafluoro-1- pentene HFC-1429sC₅HF₉ HFC-1429mzt (CF₃)₂C═CHCF₃ 1,1,1,4,4,4-hexafluoro-2-(trifluoromethyl)-2-butene HFC-1429myz CF₃CF═CHCF₂CF₃1,1,1,2,4,4,5,5,5-nonafluoro-2- pentene HFC-1429mzy CF₃CH═CFCF₂CF₃1,1,1,3,4,4,5,5,5-nonafluoro-2- pentene HFC-1429eyc CHF═CFCF₂CF₂CF₃1,2,3,3,4,4,5,5,5-nonafluoro-1- pentene HFC-1429czc CF₂═CHCF₂CF₂CF₃1,1,3,3,4,4,5,5,5-nonafluoro-1- pentene HFC-1429cycc CF₂═CFCF₂CF₂CHF₂1,1,2,3,3,4,4,5,5-nonafluoro-1- pentene HFC-1429pyy CHF₂CF═CFCF₂CF₃1,1,2,3,4,4,5,5,5-nonafluoro-2- pentene HFC-1429myyc CF₃CF═CFCF₂CHF₂1,1,1,2,3,4,4,5,5-nonafluoro-2- pentene HFC-1429myye CF₃CF═CFCHFCF₃1,1,1,2,3,4,5,5,5-nonafluoro-2- pentene HFC-1429eyym CHF═CFCF(CF₃)₂1,2,3,4,4,4-hexafluoro-3- (trifluoromethyl)-1-butene HFC-1429cyzmCF₂═CFCH(CF₃)₂ 1,1,2,4,4,4-hexafluoro-3- (trifluoromethyl)-1-buteneHFC-1429mzt CF₃CH═C(CF₃)₂ 1,1,1,4,4,4-hexafluoro-3-(trifluoromethyl)-2-butene HFC-1429czym CF₂═CHCF(CF₃)₂1,1,3,4,4,4-hexafluoro-3- (trifluoromethyl)-1-butene HFC-1438s C₅H₂F₈HFC-1438fy CH₂═CFCF₂CF₂CF₃ 2,3,3,4,4,5,5,5-octafluoro-1-penteneHFC-1438eycc CHF═CFCF₂CF₂CHF₂ 1,2,3,3,4,4,5,5-octafluoro-1-penteneHFC-1438ftmc CH₂═C(CF₃)CF₂CF₃ 3,3,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene HFC-1438czzm CF₂═CHCH(CF₃)₂1,1,4,4,4-pentafluoro-3- (trifluoromethyl)-1-butene HFC-1438ezymCHF═CHCF(CF₃)₂ 1,3,4,4,4-pentafluoro-3- (trifluoromethyl)-1-buteneHFC-1438ctmf CF₂═C(CF₃)CH₂CF₃ 1,1,4,4,4-pentafluoro-2-(trifluoromethyl)-1-butene HFC-1447s C₅H₃F₇ HFC-1447fzy (CF₃)₂CFCH═CH₂3,4,4,4-tetrafluoro-3-(trifluoromethyl)- 1-butene HFC-1447fzCF₃CF₂CF₂CH═CH₂ 3,3,4,4,5,5,5-heptafluoro-1-pentene HFC-1447fyccCH₂═CFCF₂CF₂CHF₂ 2,3,3,4,4,5,5-heptafluoro-1-pentene HFC-1447czcfCF₂═CHCF₂CH₂CF₃ 1,1,3,3,5,5,5-heptafluoro-1-pentene HFC-1447mytmCF₃CF═C(CF₃)(CH₃) 1,1,1,2,4,4,4-heptafluoro-3-methyl-2- buteneHFC-1447fyz CH₂═CFCH(CF₃)₂ 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene HFC-1447ezz CHF═CHCH(CF₃)₂1,4,4,4-tetrafluoro-3-(trifluoromethyl)- 1-butene HFC-1447qztCH₂FCH═C(CF₃)₂ 1,4,4,4-tetrafluoro-3-(trifluoromethyl)- 2-buteneHFC-1447syt CH₃CF═C(CF₃)₂ 2,4,4,4-tetrafluoro-3-(trifluoromethyl)-2-butene HFC-1456s C₅H₄F₆ HFC-1456szt (CF₃)₂C═CHCH₃3-(trifluoromethyl)-4,4,4-trifluoro-2- butene HFC-1456szy CF₃CF₂CF═CHCH₃3,4,4,5,5,5-hexafluoro-2-pentene HFC-1456mstz CF₃C(CH₃)═CHCF₃1,1,1,4,4,4-hexafluoro-2-methyl-2- butene HFC-1456fzce CH₂═CHCF₂CHFCF₃3,3,4,5,5,5-hexafluoro-1-pentene HFC-1456ftmf CH₂═C(CF₃)CH₂CF₃4,4,4-trifluoro-2-(trifluoromethyl)-1- butene FC-151-12s C₆F₁₂FC-151-12c CF₃(CF₂)₃CF═CF₂ 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluoro-1-hexene (or perfluoro-1-hexene) FC-151-12mcy CF₃CF₂CF═CFCF₂CF₃1,1,1,2,2,3,4,5,5,6,6,6-dodecafluoro- 3-hexene (or perfluoro-3-hexene)FC-151-12mmtt (CF₃)₂C═C(CF₃)₂ 1,1,1,4,4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene FC-151-12mmzz (CF₃)₂CFCF═CFCF₃1,1,1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl)-2-pentene HFC-152-11sC₆HF₁₁ HFC-152-11mmtz (CF₃)₂C═CHC₂F₅ 1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene HFC-152-11mmyyz (CF₃)₂CFCF═CHCF₃1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl)-2-pentene HFC-1549sC₆H₃F₉ PFBE CF₃CF₂CF₂CF₂CH═CH₂ 3,3,4,4,5,5,6,6,6-nonafluoro-1- (orHFC-1549fz) hexene (or perfluorobutylethylene) HFC-1549fztmmCH₂═CHC(CF₃)₃ 4,4,4-trifluoro-3,3-bis(trifluoromethyl)- 1-buteneHFC-1549mmtts (CF₃)₂C═C(CH₃)(CF₃) 1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene HFC-1549fycz CH₂═CFCF₂CH(CF₃)₂2,3,3,5,5,5-hexafluoro-4- (trifluoromethyl)-1-pentene HFC-1549mytsCF₃CF═C(CH₃)CF₂CF₃ 1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl- 2-penteneHFC-1549mzzz CF₃CH═CHCH(CF₃)₂ 1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene HFC-1558s C₆H₄F₈ HFC-1558szyCF₃CF₂CF₂CF═CHCH₃ 3,4,4,5,5,6,6,6-octafluoro-2-hexene HFC-1558fzcccCH₂═CHCF₂CF₂CF₂CHF₂ 3,3,4,4,5,5,6,6-octafluoro-2-hexene HFC-1558mmtzc(CF₃)₂C═CHCF₂CH₃ 1,1,1,4,4-pentafluoro-2- (trifluoromethyl)-2-penteneHFC-1558ftmf CH₂═C(CF₃)CH₂C₂F₅ 4,4,5,5,5-pentafluoro-2-(trifluoromethyl)-1-pentene HFC-1567s C₆H₅F₇ HFC-1567ftsCF₃CF₂CF₂C(CH₃)═CH₂ 3,3,4,4,5,5,5-heptafluoro-2-methyl-1- penteneHFC-1567szz CF₃CF₂CF₂CH═CHCH₃ 4,4,5,5,6,6,6-heptafluoro-2-hexeneHFC-1567fzfc CH₂═CHCH₂CF₂C₂F₅ 4,4,5,5,6,6,6-heptafluoro-1-hexeneHFC-1567sfyy CF₃CF₂CF═CFC₂H₅ 1,1,1,2,2,3,4-heptafluoro-3-hexeneHFC-1567fzfy CH₂═CHCH₂CF(CF₃)₂ 4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene HFC-1567myzzm CF₃CF═CHCH(CF₃)(CH₃)1,1,1,2,5,5,5-heptafluoro-4-methyl-2- pentene HFC-1567mmtyf(CF₃)₂C═CFC₂H₅ 1,1,1,3-tetrafluoro-2-(trifluoromethyl)- 2-penteneFC-161-14s C₇F₁₄ FC-161-14myy CF₃CF═CFCF₂CF₂C₂F₅1,1,1,2,3,4,4,5,5,6,6,7,7,7- tetradecafluoro-2-heptene FC-161-14mcyyCF₃CF₂CF═CFCF₂C₂F₅ 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene HFCs-162-13s C₇HF₁₃ HFC-162-13mzyCF₃CH═CFCF₂CF₂C₂F₅ 1,1,1,3,4,4,5,5,6,6,7,7,7- tridecafluoro-2-hepteneHFC162-13myz CF₃CF═CHCF₂CF₂C₂F₅ 1,1,1,2,4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene HFC-162-13mczy CF₃CF₂CH═CFCF₂C₂F₅1,1,1,2,2,4,5,5,6,6,7,7,7- tridecafluoro-3-heptene HFC-162-13mcyzCF₃CF₂CF═CHCF₂C₂F₅ 1,1,1,2,2,3,5,5,6,6,7,7,7- tridecafluoro-3-hepteneCyclic Cyclo[—CX═CY(CXY)_(n)—] fluoroolefins HFC-C1316cccyclo-CF₂CF₂CF═CF— 1,2,3,3,4,4-hexafluorocyclobutene HFC-C1334cccyclo-CF₂CF₂CH═CH— 3,3,4,4-tetrafluorocyclobutene HFC-C1436cyclo-CF₂CF₂CF₂CH═CH— 3,3,4,4,5,5,-hexafluorocyclopentene HFC-C1418ycyclo-CF₂CF═CFCF₂CF₂— 1,2,3,3,4,4,5,5- octafluorocyclopenteneFC-C151-10y cyclo-CF₂CF═CFCF₂CF₂CF₂— 1,2,3,3,4,4,5,5,6,6-decafluorocyclohexene

The compounds listed in Table 2 are available commercially or may beprepared by processes known in the art.

In addition to the inventive compounds described above, thebromine-containing fluorocarbons or hydrofluorocarbons presented inTable 3 can be used as aerosol propellants.

TABLE 3 Structure Chemical Names CF₂═CHCF₂Br3-bromo-1,1,3,3-tetrafluoropropene CF₂═CFCBrH₂3-bromo-1,1,2-trifluoropropene CHF═CBrCF₃2-bromo-1,3,3,3-tetrafluoropropene CHF═CHCBrF₂3-bromo-1,3,3-trifluoropropene CHF═CBrCHF₂2-bromo-1,3,3-trifluoropropene CHBr═CFCF₃1-bromo-2,3,3,3-tetrafluoropropene CHBr═CHCF₃1-bromo-3,3,3-trifluoropropene CH₂═CBrCF₃ 2-bromo-3,3,3-trifluoropropeneCH₂═CFCBrF₂ 3-bromo-2,3,3-trifluoropropene CFBr═CHCF₃1-bromo-1,3,3,3-tetrafluoropropene CFBr═CFCF₃ 1-bromopentafluoropropeneCH₂═CBrCF₂CF₃ 2-bromo-3,3,4,4,4-pentafluoro-1-butene CHBr═CHCF₂CF₃1-bromo-3,3,4,4,4-pentafluoro-1-butene CH₂═CHCF₂CF₂Br4-bromo-3,3,4,4-tetrafluoro-1-butene CH₂═CHCBrFCF₃3-bromo-3,4,4,4-tetrafluoro-1-butene CF₃CBr═CFCF₃2-bromo-1,1,1,3,4,4,4-heptafluoro-2-butene CH₃CBr═CHCF₃2-bromo-4,4,4-trifluoro-2-butene CF₃CBr═CHCH₃2-bromo-1,1,1-trifluoro-2-butene (CF₃)₂C═CHBr1-bromo-3,3,3-trifluoro-2-(trifluoromethyl)-propene CF₃CF═CBrCF₂CF₃3-bromo-1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene E-CHF₂CBr═CFC₂F₅E-2-bromo-1,1,3,4,4,5,5,5-octafluoro-2-pentene Z-CHF₂CBr═CFC₂F₅Z-2-bromo-1,1,3,4,4,5,5,5-octafluoro-2-pentene CF₂═CBrCHFC₂F₅2-bromo-1,1,3,4,4,5,5,5-octafluoro-1-pentene CHBr═CF(CF₂)₂CHF₂1-bromo-2,3,3,4,4,5,5-heptafluoro-1-pentene CH₂═CBrCF₂C₂F₅2-bromo-3,3,4,4,5,5,5-heptafluoro-1-pentene CF₂═CHCF₂CH₂CBrF₂5-bromo-1,1,3,3,5,5-hexafluoro-1-pentene (CF₃)₂CFCBr═CH₂2-bromo-3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene CF₂═C(CH₂Br)CF₃2-(bromomethyl)-1,1,3,3,3-pentafluoropropene CH₂═C(CBrF₂)CF₃2-(bromodifluoromethyl)-3,3,3-trifluoropropene (CF₃)₂CHCH═CHBr1-bromo-4,4,4-trifluoro-3-(trifluoromethyl)-1-butene (CF₃)₂C═CHCH₂Br4-bromo-1,1,1-trifluoro-2-(trifluoromethyl)-2-butene CH₂═CHCF(CF₃)CBrF₂3-(bromodifluoromethyl)-3,4,4,4-tetrafluoro-1-butene CF₃CF₂CF₂CBr═CH₂2-bromo-3,3,4,4,5,5,5-heptafluoro-1-pentene CF₃(CF₂)₃CBr═CH₂2-bromo-3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene

The compounds listed in Table 3 are available commercially or may beprepared by processes known in the art.

1-Bromo-3,3,4,4,4-pentafluoro-1-butene may be prepared by a three stepsequence beginning with reaction of phosphorous tribromide with3,3,4,4,4-pentafluoro-1-butanol to give4-bromo-1,1,1,2,2-pentafluorobutane. Thermal bromination of4-bromo-1,1,1,2,2-pentafluorobutane at 350-400° C. gives4,4-dibromo-1,1,1,2,2-pentafluorobutane which may in turn be heated withpowdered potassium hydroxide to give the desired bromobutene.

2-Bromo-3,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene may be preparedby addition of bromine to 3,4,4-tetrafluoro-3-(trifluoromethyl)-1-butenefollowed by treatment of the resulting dibromide with ethanolicpotassium hydroxide.

Many of the compounds of Formulas I, Table 1, Table 2 and Table 3 existas different configurational isomers or stereoisomers. When the specificisomer is not designated, the disclosure herein is intended to includeall single configurational isomers, single stereoisomers, or anycombination thereof. For instance, CF₃CH═CHCF₃ is meant to represent theE-isomer, Z-isomer, or any combination or mixture of both isomers in anyratio. Another example is C₂F₅CF₂CH═CH—CF₂C₂F₅, by which is representedthe E-isomer, Z-isomer, or any combination or mixture of both isomers inany ratio.

Aerosol propellants may comprise a single compound as listed, forexample, in Table 2, or may comprise a combination of compounds fromTable 2 or, alternatively, a combination of compounds from Table 1,Table 2, Table 3, and/or Formula I.

The amount of the fluorocarbons (FCs) or HFCs contained in the presentcompositions (from, e.g., Formula I, Table 1, or Table 2, or Table 3)can vary widely, depending the particular application, and compositionscontaining more than trace amounts and less than 100% of the compoundare within broad the scope of the present disclosure. Preferably, thecompositions have a Global Warming Potential (GWP) of not greater than150, more preferably not greater than 100, and even more preferably notgreater than 75. As used herein, “GWP” is measured relative to that ofcarbon dioxide and over a 100-year time horizon, as defined in “TheScientific Assessment of Ozone Depletion, 2002, a report of the WorldMeteorological Association's Global Ozone Research and MonitoringProject,” which is incorporated herein by reference.

The present compositions also preferably have an Ozone DepletionPotential (ODP) of not greater than 0.05, more preferably not greaterthan 0.02 and even more preferably about zero. As used herein, “ODP” isas defined in “The Scientific Assessment of Ozone Depletion, 2002, Areport of the World Meteorological Association's Global Ozone Researchand Monitoring Project,” which is incorporated herein by reference.

The compositions may be prepared by any convenient method to combine thedesired amounts of the individual components. A preferred method is toweigh the desired component amounts and thereafter combine thecomponents in an appropriate vessel. Agitation may be used, if desired.

The propellants may comprise a single compound as listed, for example,in Table 1, or may comprise a combination of compounds of Formula I,Table 1, Table 2, and/or Table 3. Additionally, many of the compoundsdescribed herein may exist as different configurational isomers orstereoisomers. The disclosure herein is intended to include all singleconfigurational isomers, single stereoisomers, or any combinationthereof. For instance, F11E is meant to represent the E-isomer,Z-isomer, or any combination or mixture of both isomers in any ratio.Another example is F33E, by which is represented the E-isomer, Z-isomer,or any combination or mixture of both isomers in any ratio.

Preferably, the propellants disclosed herein have a Global WarmingPotential (GWP) of not greater than 150, more preferably not greaterthan 100, and even more preferably not greater than 75. As used herein,“GWP” is measured relative to that of carbon dioxide and over a 100-yeartime horizon, as defined in “The Scientific Assessment of OzoneDepletion, 2002, a report of the World Meteorological Association'sGlobal Ozone Research and Monitoring Project,” which is incorporatedherein by reference.

The present compositions also preferably have an Ozone DepletionPotential (ODP) of not greater than 0.05, more preferably not greaterthan 0.02 and even more preferably about zero. As used herein, “ODP” isas defined in “The Scientific Assessment of Ozone Depletion, 2002, Areport of the World Meteorological Association's Global Ozone Researchand Monitoring Project,” which is incorporated herein by reference.

The compositions may be prepared by any convenient method to combine thedesired amounts of the individual components. A preferred method is toweigh the desired component amounts and thereafter combine thecomponents in an appropriate vessel. Agitation may be used, if desired.

The propellant composition comprises, more preferably consistsessentially of, and, even more preferably, consists of compositionsdisclosed herein. The active ingredient to be sprayed together withinert ingredients, solvents, and other materials may also be present inthe sprayable mixture. Preferably, the sprayable composition is anaerosol.

Another embodiment of the present disclosure provides a process forproducing aerosol products comprising the step of adding a compositionas disclosed herein to active ingredients in an aerosol container,wherein said composition functions as a propellant.

The compositions are capable of providing nonflammable, liquefied gaspropellant and aerosols that do not contribute substantially to globalwarming. The present compositions can be used to formulate a variety ofindustrial aerosols or other sprayable compositions such as contactcleaners, dusters, lubricant sprays, mold release sprays, and the like,and consumer aerosols such as personal care products (such as, e.g.,hair sprays, deodorants, and perfumes), household products (such as,e.g., waxes, polishes, pan sprays, room fresheners, and householdinsecticides), and automotive products (such as, e.g., cleaners andpolishers), as well as medicinal materials such as anti-asthma andanti-halitosis medications. Examples of this includes metered doseinhalers (MDIs) for the treatment of asthma and other chronicobstructive pulmonary diseases and for delivery of medicaments toaccessible mucous membranes or intranasally.

All such products utilize the pressure of a propellant gas or a mixtureof propellant gases (i.e., a propellant gas system) to expel activeingredients from the container. For this purpose, most aerosols employliquefied gases which vaporize and provide the pressure to propel theactive ingredients when the valve on the aerosol container is pressedopen.

The medicinal aerosol and/or propellant and/or sprayable compositions inmany applications include, in addition to a compound disclosed herein, amedicament such as a beta-agonist, a corticosteroid or other medicament,and, optionally, other ingredients, such as surfactants, solvents, otherpropellants, flavorants, and other excipients. The compositionsdisclosed herein, unlike many compositions previously used in theseapplications, have good environmental properties and are not consideredto be potential contributors to global warming. The present compositionstherefore provide in certain preferred embodiments substantiallynonflammable, liquefied gas propellants having very low GWPs.

All of the compositions and methods disclosed and claimed herein can bemade and executed without undue experimentation in light of the presentdisclosure. While the compositions and methods disclosed herein havebeen described in terms of preferred embodiments, it will be apparent tothose of skill in the art that variations may be applied to thecompositions and methods and in the steps or in the sequence of steps ofthe method described herein without departing from the concept, spirit,and scope of the present disclosure. More specifically, it will beapparent that certain agents which are chemically related may besubstituted for the agents described herein while the same or similarresults would be achieved. All such similar substitutes andmodifications apparent to those skilled in the art are deemed to bewithin the spirit, scope, and concept of the present disclosure asdefined by the appended claims.

EXAMPLES

The present disclosure is further defined in the following Examples. Itshould be understood that these Examples, while indicating preferredembodiments, are given by way of illustration only. From the abovediscussion and these Examples, one skilled in the art can ascertain thepreferred features, and without departing from the spirit and scopethereof, can make various changes and modifications to adapt it tovarious uses and conditions.

Example 1 55% VOC Hair Spray

A 55% VOC (volatile organic compound) hairspray was formulated asfollows:

Wt % Octylacrylamide/acrylates/butylaminoethyl  5.0 methylacrylatecopolymer (National Starch Amphomer LV-71) AMP(2-amino-2-methyl-1-propanol)  1.0 Water  3.5 Ethanol 55.0 Propellant35.0 Vapor Pressure @ 70 F. 40 psig

The formulation was one phase indicating complete miscibility and showedgood spray patterns and delivery.

Example 2 Air Freshener

An air freshener was formulated as follows:

Wt % Fragrance (Dragoco 0/716873 mixed flowers scent)  1.0 Water  4.0Ethanol 30.0 Propellant 65.0 Vapor Pressure @ 70 F. 48 psig

The formulation was one phase indicating complete miscibility and showedgood spray patterns and delivery.

Example 3 Fragrance

A fragrance was formulated as follows:

Wt % Perfume (Dragoco 0/716873 mixed flowers scent)  3.0 Water 15.0Ethanol 70.0 Propellant 12.0 Vapor Pressure @ 70 F. 17 psig

The formulation was one phase indicating complete miscibility and showedgood spray patterns and delivery.

Example 4 Aerosol Antiperspirant

An aerosol antiperspirant was formulated as follows:

Wt % Aluminum chlorohydrate 10.0 (Reheis Activated ACH ModifiedR277-265A) Isopropyl myristate  6.0 Silicone fluid DC-344  6.0Quaternium-18 hectorite (Rheox Bentone 38)  0.5 Ethanol  2.0 Propellant75.0 Propellant 12.0 Vapor Pressure @ 70 F. 48 psig

The formulation provided good suspendability for the antiperspirantactive, showed good spray patterns and delivery, and did not plug thevalve.

Similar formulations can also be developed for household disinfectants,insect foggers, and spray paints using the compositions of the presentdisclosure.

We claim:
 1. An aerosol dispensing system comprising a sealed containerequipped with an aerosol dispensing valve and a propellant, wherein saidpropellant comprises at least one hydrofluorolefin selected from thegroup consisting of: CF₃CH═CHCF₃, CF₃CH═CHC₂F₅, CF₃CH═CHCF₂C₂F₅,CF₃CH═CHCF(CF₃)₂, C₂F₅CH═CHC₂F₅, CF₃CH═CH(CF₂)₃CF₃, CF₃CH═CHCF₂CF(CF₃)₂,CF₃CH═CHCF(CF₃)C₂F₅, CF₃CH═CHC(CF₃)₃, C₂F₅CH═CHCF₂C₂F₅, andC₂F₅CH═CHCF(CF₃)₂.
 2. The aerosol dispensing system of claim 1, whereinthe propellant consists essentially of the hydrofluorocarbon.
 3. Theaerosol dispensing system of claim 1, wherein the propellant has a vaporpressure in a range of from about 138 to about 621 kPA at 21° C.
 4. Theaerosol dispensing system of claim 1, wherein the aerosol is a cleaner,duster, personal care product, automotive product, or medicament.